Copperable disazo dyestuffs



Patented July 18, 1950 2,515,546 COPPERABLIEDIYSAZO DYESTUFFS Werner Bossard, Riehen, near Basel, and Marcel Reding, Basel, Switzerland, assignors to J. R. Gelgy A. G., Basel, Switzerland, a Swiss firm No brawing. Application April 27, 1948, Serial No. 23,626. In Switzerland May 2, 1947 4 Claims. (Cl. 260-176) 1 v The present invention is concerned with th manufacture of copperable disazo dyestuffs which give dyeings with excellent fastnes properties on cellulose fibres.

The copperable polyazo dyestuffs have the advantagesof' very simple methods of manufacture, fastness to light which is oftenvery good and of cheapness. These dyestuff have greatly increased in importancebecause of wider applicability. This is especially true since the successful production of navy blue" to black dyestuffs whose dyeings on celluloseshow a fastness, even to repeated soap-washing, allowing them to compete forcertain purposes with even the'vat dyestuffs which, although somewhat superior, are expensive and difficultto dye. l

The present invention is a valuable contribution to this group of copperable polyazo dyestuffs with outstanding fastness properties when wet, since it permits of the manufacture of yellow, copperable disazo dyestufis whose after-coppered cellulose dyeings completely satisfy exacting requirements for wet-fastness properties after repeated soap-washing.

It has been found that by coupling an unsulfonated 4 :4 di acetoacetylamino diphenyl compound, which may also contain in 3:3'-position the usual simple substituents found in azo dyestuffs, such as alkyl and alkoxy groups or halogen atoms, on the one hand with one mol of .an o-hydroxydiazo compound of the benzene series and on the other hand with one mol of a diazotised amine of the general formula A means an aryl radical of the benzene series and X means an OH or COOH group as metal-complex forming group there are obtained substantive disazo dyestuffs which give after-coppered dyeings on cellulose fibres having extraordinary fastness even after repeated soap-washing. It is advantageous to choose the components so that the disazo dyestuffs formed contain at least one sulfonic acid group, although the presence of two carboxyl groups is sufficient. I The disazo dyestuffs of the invention are therefore characterised in that they contain, linked with the acetoacetyl radicals of the 4:4 di acetoacetylamino diphenyl compounds, atleast oneo-hydroxyphenyl group, while the second arylazo group can also be a hydroxyphenylazo group, or an o-carboxy-phe'nylazo groupi'" W The unsulfonated' 4:4 di acetoacetylaminodiphenyl compound used in the invention are obtained by methods known' perse from unwherein sulfonated 4:4 diaminodiphenyl compounds usual in dye chemistry for making substantive azo dyestuffs (cflMayer, Fl, Chemie der organi-' schen Farbstoife, 3rd edn., Berlin, 1934, p. 54; Fierz-David, H. E., Kiinstliche Organische Farb stoffe, Berlin, 1926, p. 1'79; Ullmann, F., Enzyklopadie der technischen Chemie, 2nd ednl, Berlin," vol. 2, 1926, p. 40) by reacting with aceto'acetic acid esters or diketene. Particularly 'valuable disazo dyestuffs distinguished by gooddrawing power on cellulose fibres and outstanding fas'tnes's to washing are produced on'using unsulfonated 4 4-di-acetoacetyl-amino-diphenyl compounds substituted in the 3:3-positions of the diphenyl radical. When the 3:3-substituent is methyl or halogen, the dyestuffs generally yield coloristically interesting yellowish shades, while those with alkoxy groups in the 3:3-positions give fine reddish yellow tones with extremelygood fastness to Washing, surpassing in this respect dyestuffs either unsubstituted or with other substituents in the diphenyl radical.

As already mentioned, the disazo dyestuffs according to the invention should containat least one sulfonic acid group; more than'two sulfonic acid groups in the dyestuif molecule, however, give products with distinctly poorer wet-fastness properties. H Especially valuable are dyestuffs with only one sulfonic acid group. Since the sulfonic acid radical can be present in only one of the two diazo components, this valuable group of the new, fast to washing, copperable dyestuffs is characterised in all cases by asymmetry with respect to the sulfonic acid grouping. Dyestuffs with o-aminophenol-monosulfonic acids, which may, like all the diazo components mentioned herein after, contain further substituents usualin .azo dyestuffs, as first diazo component andunsub fonated anthranilic acids as the second, leadto yellow coppered cellulose dyeings, whereas with unsulfonated o-aminophenols the coppered dyeings are golden-yellow; Anthranilic monosulfonic acids .as the first, and unsulfonated o-aminophenols as the second diazo component yield practically equivalent yellow, coppered cellulose dyeings. As particularly valuable diazo components there may further be mentioned: the i6- acylamino 2- amino 1 hydroxybenzene 4" sulfonic acids, especially 6 benzoylamino -'2 amino-1-hydroxybenzene-4-su1fonic acid and also 6 acetylamino 2 amino 1 hydroxybenzene-4-sulfonic acid and the 5-acyl'amino-2- aminobenzoic acids, especially 5-acetyla'minoan 5-benzoylamino-2-aminobenzoic acid. The majority of dyestuffs with two sulfonic acid groups in the molecule, which can be either symmetrical or unsymmetrical with respect to these radicals are not quite up to the standard of the first mentioned type. However, the 6- benzoylamino 2 amino 1 hydroxybenzene f 4 sulfonic acid cited above gives symmetrical disazo dyestuff-disulfonic acids which :yield coppered cellulose dyeings with very good fastness prop- OH I a damaging effect on fastnesstowater.

serviceable solubility in water.

The most valuable dyestuffs with regard to the wet-fastness properties of the after-coppered.cel lulose dyeings are, as can be seen from the above, the unsymmetrical disazodyestuiT-monosulfonic acids. from 6-benzoy1amino-2-aminoel hydroxybenzenel-sulfonic acid asfirst diazo component and unsulfonated o-aminophenols or unsulfonated anthranilic acids as second, the E-acety laminoand -benzoylamino-Z-amino-benzoic acids being specially suitable; The important part played by 3:3-dimethoxy or 3:3"-'dichloro substitution in the diphenyl radicals has i also been already mentioned.

Thetwo diazo components can be coupled with the 4 4di-acetoacetylamino-diphenyl compounds in any order but it is advisable on practical grounds to use a sulfonated diazo compound first. The. disazo dyestuffs of the invention can be coppered either in the dyebath or in a fresh bath with. the usual copper salts such as, for example, copper sulfate or copper acetate, in a neutral or weakly acid medium. When necessary copper compounds stable to alkalies canbe used, such as are obtained, for example, on treating copper sulfate with sodium tartrate in a hath made alkaline with soda. The after-treatment with copperising media changes the shade of the cellulose dyeings only slightly, but fastness to washing, light and alkalis is considerably improved.

COOHs Yellow copperable disazo dyestufis for cellulose fibres from one mol of a sulfo-anthranilic acid and one mol of an unsulfonated anthranilic acid as diazo components and 4:4-di-aceto-acetylamino-3:3'-dimethyl-diphenyl as coupling component have already been described in the U. S. Patent No. 1,879,223. The disazo dyestuffs of the present invention are superior tothese di-ocarboxyaryl-azo dyestuffs, particularly as regards wet-fastness properties, but also in fastness to alkalis, acids and to light.

The following examples serve tov illustrate the invention, without limitin it however. Parts are given by weight and temperatures are indegrees Centigrade.

Example 1 18.9 parts I of 2--amino-1-hydroxybenZene-4- sulfonic acid are-diazotised in the usual Way with 6.9 parts of sodium nitrite and added dropwise in the cold to a solution 0133 parts of 4:4- diaceto-acetylamino-3 :3 -di1nethy1-1 l -diphenyl in 400 parts of water, 10 parts of caustic soda lye and 20 parts of soda. After coupling is completed, parts of soda in 80 parts of water are COOH CHr-CO H3 is precipitated out with common salt, filtered and dried. It is a yellowish-brown powder which dissolves in water and concentrated sulfuric acid to give a yellow solution. It gives after-coppered dyeings with cotton, staple fibre, viscose, hemp or jute in yellow tones with excellent fastness properties.

' If, instead of the 38 parts of 4:4='-diacetoacetyl-1 amino-3-:3-dimethy1-1zl' diphenyl in the above example there are used 33.2 parts of 414'- diacetoacetylamino-l:1-diphenyl, 41.2 parts of 4:4 diacetoacetylamino 3:3 dimethoxy 1:1 diphenyl or 42.1 parts of 4:4'-diacetoacetyl'amino-3 3-dicl11oro-1 1-diphenyl, then dyestuffs with similar properties are obtained.

35 Example 2 I 30.8 parts of 6-benzoylamino-2-amino-1-hydroxybenzene-e-sulfonic acid are dissolved togetherwith 8 parts of soda in 250 parts of water. 6.9 parts of sodium nitrite are then mixed in and the whole added dropwise in the cold to parts concentrated hydrochloric acid. and 50 parts of water. The suspension of the diazonium compound so obtained is then mixed with a cold alkaline solution of 41.2 parts of 4:4-diacetoacetylamino-3 3'-dimethoxy-1 1'-diphenyl in the presence of 20 parts of soda. The monoazo dyestuil forms rapidly. To it are added 20 parts of soda and the diazonium compound, prepared in the usual. way, from 18.7 parts of Z-amino-lhydroxybenzene-'l-methylsu1fone. After coupling is complete the disazo dyestuff produced, having the formula OH COCH;

s olom is separated out with common salt, filtered. off and dried. It is a brown powder, dissolving in water and concentrated sulfuric acid to give a yellow solution and dyes after-coppered fibres of natural or regenerated cellulose in golden-yellow shades. The dyeings have excellent fastness properties.

' Similar golden-yellow dyestuffs with equally good fastness properties. are obtained if instead of 18.? parts of 2-amino-l-hydroxybenzenesmethylsulfone there are used 10.9 parts of 2 amino-l-hydroxybenzene, 12.3 parts of 4- or 5- methyl-2-amino-l-hydroxybenzene, 18.8 parts of 2-amino-1-hydroxybenzene-4-su1fonic acid amide, 20.2 parts of 2 amino-1-hydroxybenzene-4- sulfonic acid-monomethylamide, 21.6 parts of 2- amino 1 hydroxybenzene 4 sulfonic acid dimethylamide, 14.35 parts of 4-ohloro-2-aminol-hydroxybenzene, 15.4 parts of 4-nitro-2-aminol-hydroxybenzene, 19.9 parts of 2:4-dinitro-6- amino-l-hydroxy-benzene, 15.3 parts of 2-amino- 1-hydroxybenzene-i-carboxylic acid, 30.8 parts of 4-benzoyl-amino-2-amino-l-hydroxybenzene- 6-su1fonic acid. The other preparative details are exactly as described in the above example.v

7 Example 3 23.3 parts of 2-amino-1-hydroxybenzene-4- sulfonic acid-G-carboxylic acid are diazotised in the usual manner and the diazonium solution obtained is coupled at -5 with an alkaline solution of 42.1 parts of 4:4'-diacetoacetyl-amino- SQaH 3:3'-dichloro-1:1'-diphenyl and 20 parts of soda. The monoazo dyestufi solution is then mixed with 20 parts of soda and the diazonium compound from 18.8 parts of 2-amino-1-hydroxybenzene-4-sulfonic acid amide. After a short time the disazo dyestufi of the formula is formed and separated by adding common salt. When dried it is a brown powder giving a yellow solution in water and concentrated sulfuric acid. It produces fast, yellow after-coppered dyeings on cotton and staple fibre.

Similar yellow dyestufis with similar properties are obtained if the 23.3 parts of 2-amino-1- hydroxybenzene -4- sulfonic acid 6 carboxylic acid of the above example are replaced by the same amount of 2-amino-1-hydroxybenzene-6- sulfonic acid-4-carboxy1ic acid, 18.9 parts of 2- amino-1-hydroxybenzene-4-sulfonic acid, 22.35 parts of 6-chloro-2-amino-1-hydroxybenzene-4- sulfonic acid, 20.3 parts of 4- or 6-methyl-2- amino-l-hydroxybenzene-S- or -4-sulfonic acid, 23.4 parts of 6-nitro-2-amino-I-hydroxybenzene- 4-sulfonic acid, 24.6 parts of 6- or 4-acety1amino- 2-amino-1-hydroxybenzene 4 or 6 sulfonic acid, 30.8 parts of 4-benzoylamino-2-amino-1- hydroxybenzene-6-sulfonic acid, 26.9 parts of 2 amino-1-hydroxybenzene-4:fi-disulfonic acid or 21.7 parts of 2-aminobenzene-l-carboxylio acid- 4- or --sulfonic acid.

On the other hand, it 41.2 parts of 4:4'-diacetoacetylamino-3:3'-dimethoxy-1:1 diphenyl are used for the dyestuffs enumerated above instead of 42.1 parts of 4:4'-diacetoacetylamino-3:3- diohloro-1:1'-diphenyl, then a. somewhat more greenish yellow but with the same excellent fastness properties is obtained.

Example 4 COCH;

an alkaline solution of 42.1 parts of 4:4'-diacet0acetylamino-3 3' -dich1oro-1 1 -diphenyl and 6 20 parts of soda. To the solution of monoazo dyestuff are added 10 parts of sodium bicarbonate and the diazonium compound from 19.4 parts of 5-acetylamino-2-aminobenzene-1-car- 'boxylic acid. The disazo dyestufi. formed, having the formula coon CH:

is precipitated out with common salt, filtered and dried. It is a yellowish brown powder whose solution in water and concentrated sul- :furic acid is yellow in colour. The after-coppered yellow dyeings on cellulose fibres have excellent fastness properties.

0 11 C O-CH:1

AOQNHZ Similar dyestufi's are obtained in the same way if, instead of 19.4 parts of 5-acetylamino-2 aminobenzene-l-carboxylic acid there are used 13.7 parts of Z-aminobenzene-l-carboxylic acid, 17.15 parts of 4- or 5-chloro-2-aminobenzene-1- carboxylic acid, 18.1 parts of Z-aminobenzene- 1:4- or --dicarboxylic acid, 21.6 parts of 2- aminobenzene-l-carboxylic acid-5-sulfonic acid amide, 23.0 parts of 2-aminobenzene-l-canboxylic acid-5-sulfonic acid monomethylamide, 24.4 parts of 2-aminobenzene-1-carboxylic acid-5- sulfonic acid dimethylamide, 35.2 parts of 2-,- aminobenzene-1-carboxylic acid-5-sulfonic acidphenylamide-4-hydroxy-3-carboxylic acid or 18.7 parts of 2-aminonaphthalene-3-carboxylic acid.

If in the above example the alkaline solution of 42.1 parts of 4:4'-diacetoacetylamino-3:3'q dichloro-1:1'-dipheny1 is replaced by a similar solution of 41.2 parts of 4:4'-diacetoacetylamino- 3 3'-dimethoxy-1 1-diphenyl then somewhat more reddish dyestuffs having the same outstanding fastness properties are produced.

' droxybenzene-4-sulfonic acid are diazotised as OCH; OCH;

COCH;

is precipitated out with common salt, filtered off and dried. It is a brown powder, whichdissolves in water and concentrated sulfuric acidto give a yellow solution. It dyes 'after-coppered cotton or staple fibre in fast, golden yellow shades.

, If the 61.6 parts of G-benzoylamino-Zamino- 1-hydroxybenzene-4rsulfonic acid in th above example are replaced by the same quantity of 4.- benzoylamino 2 amino 1 hydroxybenzene-B-sulfonic acid, the procedure remaining otherwise the same, then a similar dyestuff with manner. The cotton is dyed in golden-yellow shades with outstanding. fastness properties.

The following table lists further examples, serving to illustrate the present invention. The method of manufacture is the same. ,in every case as described in the above examples. The first column contains 1 the 4 4'-diacetoacetyl-aminodiphenyl compounds, while thetwo diazo comthe samegood fastness properties is obtained. in ponents are given inthe 2nd and 3rd columns.

Table Shade of the Dlazonium compound with o-group 4:4-Dlacctoacetyl-ammodiphenyl o-Hydroxy-diazomum compound after copper-ed compound. iroml f ggg i complex dyeingon cotton 1 4:y-diacetoacetyl-amino-3:3-dime- Z-amino-lhydroxy-benzene-4-Sul- 2-amino-l-hydroxybenzenc golden-yellow,

thoxyslzl diphenyl. ionic acid. Y 9 rln dn 2-angilnonaphthalene-S-carboxylic yellow. 7

am a do 6-acetylamino,2-amino-l-hydroxy- 5-acetylamino 2 aminobenzene-l- Do.

benzeue-4-sulfonic acid. carboxylic acid. 4 fin Z-amino-l-hydroxy-benzeneocar- 3:4:(i-trichloro-Z-amino-l-l1ydroxygolden-yellow.

' boxylic acid-4-sulfonic acid. benzene. t 5 4:4-diacetoacetyl-amino-l:1-diphenyl 6-benzoylamino-2-amino-l-hydroxy- 6-benzoylamino-Z-amino-l-hydroxyyellow.

bcnzenci-sulfonic acid. benzenerwillonic acid. t a an (in 2-an1dinonaphthalene-3-carboxylic 130.

am 7 (In 2-amino-l-hydr0xy-benzene-4-sul- 2-aminc-1-l1ydroxybenzene-i-sulfonic Do.

fonic acid. acidamide. 8 4:4-diacetoacotyl-amino-3:3-dido 2-aminobenzene-l-carboxylic acid Do. chloro-lzY-diphenyl.

fin do 2-amino-l-hydtoxybenzene Do. do G-acetylamino-2-amino-l-hydroxy- 2-aminobenzenc-l-carboxyllc acid- Do.

benzene--sulfonic acid. 5-sulfonic acid-monomethyl-amidc. a.-. dn Z-amino-l-hydroxybenzene- Do.

4:4-diacetoacetyl-amino-3:3 -di1;ne- 2-amino-1 -hydroxy-benzene-d-Sulfon- 2-am1nobenzene-1 carboxylic acid- Do.

thyl lzl diphenyl. ic acid amide. sulfpnlc acid. o G-benzoylamino-Z-aminoJ-hydroxy- 2I4-d1n1tro-6-amino-l-l1ydroxy-bengolden-yellow,

- benzene-4-sulfonic acid. zone. I Y I I m, dn 4- benzoylamino-2-amino-1.-hydroxyyellow.

' benzene-fi-sulfonic acid. 4:4-'diacetoacety1-amino-3:3-dichlo- 2-amino-1-hydroxy-bcnzene-etsulfon- 2 a nmonaphthalene 3 carboxylic Dc;

ro-1:1-diphenyl 1c acid. aci 1 7 4:4"- diacetoacetyl-amino-SzS -dime- 2-an ino-l-hydroxy-benzene-6-carbox- 2 aljnlnonaphthalene 3 carboxylic Do.- tl1oxyl:l-diphenyl. yllc acid--sulfonic acid. ac do G-acetylamino 2- amino l hydroxy- Zammobenzene-l-carboxylic acid Do.

benzene-i-sulfonic acid. 2-amino-1-hydroxy-benzenc-4-carbox- 4-ch1oro-2-am1no-l-hydroxybenzene golden yellow.

ylic acid-G-sullonic acid. v 2-amino-l -hydroxy-benzene-4-sulfon- Z-ammobenzene-l-carboxylic acid-5- yellow.

ic acid. 2-amino-l-hydroxy-benzene-4-carboxsulfonic acid-dimothyl-amide. 2-amino-l-hyclroxybenzene 4-carboxgolden-yellow.

ylic acid. ylic acid. dn B-aminobenzene-l-carboxylic acid yellow.

6-chloro-2-amino-l-hydroxybenzena 4-chloro-2-am1no-l hydroxybenzenc golden-yellow.

4-sulionic acid. i 2-amino-l-hydroxybenZene-fi-carbox- Z-ammobcnzene-l-carboxylic acid yellow. ylic acid--sulfonic acid. 7 i I v v 4:4-diacetoacetyl-amino-3:3-dichloro- Z-amino-l-hydroxybenzene-4-sulfonic 2flIIllIlO-1-hYdIOXYbGDZGIlG-l-Slllfolllc Do. 1:l-diphenyl. acid. acid amide. I 7 4:4 diaoetoacetyl amino 1:1- di- 6-benz0ylamino-2-amino-l-hydroxy- 2-au ino-1-hydroxybenzene-4-sulionic Do. phenyl. benzene-l-sullonic acid. amdamide. 4:4-diacetoacetyl-amino-3 :3-dimeth- 2 amino 1 hydroxybenzene 4 car- 2 ammonaphthalene 1 3 carboxylic Do.

oxy-l:1-diphel1yl. boxylic acid-G-sulfouic acid. ac do 2-arn(i1no l-hydroxybenzene-4-sulfonic Z-aminobenzene-Lcarboxylic acid D0.

aci dn dn Z-aminobenzened-carboxylic acid-B- Do.

sulfonic acid amide. do fi-acetylamino-Z-amino-l-hydroxy- Z-amino-l-hydroxybenzene golden-yellow,

benzenei-sulionic acid. 4:4 diacetoacetyl amino 3:3 di- 2-a1'nino-l-hydroxybenzene--sulfonic 2-amino-l-liydroxybenzene yellow. methyl-l'l-d.iphenyl. acid. 4 a do fi-benzoylammo-i -ammo-l-hydroxy- 2-amlno-l-hydroxybenzene-sulfonic Do.

benzenel-sulfonic acid. acid amide. a) dn dn 2-aminobenzene-l-carboxylic acid Do. 33" 4:4 diacetoacetyl amino 1:1 did -acctylamino 2-aminobcnzene 1- Do.

phenyl. carboxylic acid. j j V 34 4:4-diacetoacetyl-amino-3:3'-dimeth- 6-cl1loro-2-axnino-l-hydroxybenzcne- Z-aminobenzene-l-carboxylic acid Do.

oxy-1:1-diphenyl. 4-sulfonic acid. v 35 do 2-amino-l-hydroxybenzene-4-sulfonic 5 benzoylamino Z-aminobenzene l D 0 acid carboxylic acid. 36 -do 5-(4-methyl-benzoylamino)-2-arnino Do.

. 4:4-diacetoacetyl-amino-3:3-dichloro- 1:1'-diphenyl.

benzene-l-carboxylic acid.

1.5 parts of the dyestuff obtained according to Example 6 What We claim is:

1. A copperable disazo dyestuff corresponding to the formula Example 2 are dissolved in 3000 parts of water and 2 parts of soda. 100 parts of cotton are entered at 4050, the bath raised to BO-95 within .30 minutes, 30 parts of sodium sulfate added and idyeing continued for minutes at this temperature. The dyed goods are then rinsed cold and after-treated in a fresh bath with 2 parts of crystalline copper sulfate in 2000 parts of water and; parts of 30% acetic acid at for 30 min CO-CHa (IO-CH:

wherein X stands for a member selected from the group consisting of H, C1, CH3, and OCHs, A

standsior an aromatic radical of the benzene ser'ies which contains a sulfonic acid group and. in o-position to the azo group a hydroxyl group,

2. A copperable disazo dyestuff corresponding to the formula COOH GHrCO NH-COCH3 B stands for an aromatic radical of the benzene 3. A copperable disazo dyestuff corresponding series which contains in o-position to the azo to the formula OH OH (JO-CH: GOOH3 OaH AOzCEh group a metal complex-forming group selected 4. A copperable disazo dyestufi corresponding from the group consisting of OH and COOH. to the formula.

(JO-OH; CO-CH:

AOBH AOQH WERNER BOSSARD. MARCEL REDING.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 2,310,181 Mackenzie Feb. 2, 1943 

2. A COPPERABLE DISAZO DYESTUFF CORRESPONDING TO THE FORMULA 